Insecticidal and acaricidal methods using oximino phosphates and phosphonates

ABSTRACT

Compounds having the formula   IN WHICH X is oxygen or sulfur; Y is oxygen or sulfur; R is alkyl; R1 is alkyl; R2 is alkyl or alkoxy and R3 is (1) phenyl, or (2) mono-, di- or tri- substituted phenyl wherein the substituent is (a) nitro or (b) halogen, and their use as insecticides, and acaricides are disclosed.

United States Patent 91 Gutman INSECTIClDAL AND ACARDCIDAL METHODS USING OXIMINO PHOSPHATES AND PHOSPHONATES [75] Inventor: Arnold D. Gutman, Berkeley, Calif.

[73] Assignees Stauffer Chemical Company, New

York, NY.

22 Filed: Jan. 20, 1972' [21] App1.No.: 219,548

Related US. Application Data [62] Division of Ser No. 26,070, April 6, 1970, Pat. No.

[ 1 Apr. 10, 1973 Primary Examiner-Albert T. Meyers Assistant Examiner-Norman A. Drezin Attorney-Daniel C. Block et a1.

[ ABSTRACT Compounds having the formula R0 )"i'. Y-RK \C=NOP/ R s R in which X is oxygen or sulfur; Y is oxygen or sulfur; R is alkyl; R is alkyl; R is alkyl or alkoxy and R is 1) phenyl, or (2) mono-, dior trisubstituted phenyl wherein the substituent is (a) nitro or (b) halogen,

and their use as insecticides, and acaricides are disclosed.

6 Claims, N0 Drawings ii/ P in which X is oxygen or sulfur; Y is oxygen or sulfur;

Rv is (1) alkyl having one to four carbon atoms, preferably branched chain or methyl, more preferably ethyl and t-butyl;

R is alkyl having one to four carbon atoms, preferably methyl;

R is alkyl having one to four carbon atoms, preferably one to two carbon atoms; or alkoxy having one to four carbon atoms, preferably 1 to 2 carbon atoms;

R is (l) phenyl or (2) mono-, dior tri-substituted phenyl wherein the substituents is (a) nitro or (b) halogen, preferably chlorine, preferably mono substitution is in the meta or para positions and the substituent is halogen or nitro, di substitution is meta and para or ortho and para and the substituents are both halogen groups and tri-substitution is in the 2,4,5 position and the substituents are all halogen, preferably chlorine. Optionally, such groups as alkyl having one to four carbon atoms or (h) alkoxy having 1 to 4 carbon atoms may also be substituted on the phenyl, preferably in the meta position.

The compounds of the present invention can be prepared according to the following reactions:

1(a) R O R O X Ms B1 R s in which R, R, R and X are as defined comprising reacting a compound of the formula in which R and R are as defined with a compound of the formula XCl in which R and X are as defined. The compound recited in reaction [(a) and 1(b) where R and R are as defined can be prepared according to the general procedure stated in Belgium Pat. No. 710,649, by reaction of the appropriate xyanthate, with hydroxyl amine hydrochloride followed by reaction with the appropriate alkyl halide.

Preferably, reaction 1(a) is carried out by reacting preferably equal mole amounts of the two reactants. If an excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any desired manner but preferably, the reaction is run in a solvent such as THF by first preparing the salt of the oxime reactant with an acid acceptor such as potassium t-butoxide at room temperature, and then preferably slowly adding the dichloride reactant thereto, preferably in solution with a solvent, for example, THF, at a temperature below about 15C. for control. However, the oxime reactant can be used in place of the salt, preferably in the presence of the acid acceptor. The resulting product is recovered and purified by standard procedure. For example, the resulting product can be recovered from the reaction mixture and purifled from the reaction mixture by adding the mixture to a non-polar solvent such as benzene. The benzene mixture is then washed with water, dilute NaOl-l solution, and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous M gSO, to yield the purified product.

The novel intermediate compounds of this invention which are useful in preparing the insecticidal and acaridial compounds of this invention, for example, by reaction 1(b), heretofore described are those having the formula in which X is oxygen or sulfur; R is alkyl having one to four carbon atoms, preferably branched chain or methyl, more preferably ethyl and t-butyl; R is alkyl having 1 to 4 carbon atoms, preferably methyl; R is alkyl having one to four carbon atoms, preferably one to two carbon atoms; or alkoxy having one to four caran excess of either reactant is used, the reaction still proceeds but yields are reduced. The reactants can be combined in any manner but preferably the phosphorus-containing reactant is slowly added to the phenol or triophenol reactant in a solvent such as THE, preferably with stirring. More preferably, an alkali metal salt of the phenol or thiphenol salt is used to reduce the chance of a violent reaction. The temperature of the reaction is not critical, however, better yields are obtained by heating the reactants at reflux for a time sufficient to allow completion of the reaction. The resulting product can be recovered from the reaction mixture and purified by standard procedures. For example, the desired reaction product can be recovered from the reaction mixture by adding the mixture to a non-solvent such as benzene. The benzene mixture is then washed with water, dilute NaOl-l solution and then again by water. The benzene is evaporated after the water has been removed, for example, by treatment with anhydrous MgSO to yield the purified product.

Preparation of the compounds of this invention and the intermediate compounds of this invention are illustrated by the following examples:

EXAMPLE I O-(O-ethyl-S-methylthioformaldoximino), thiophosphonyl chloride 22.4 grams (0.2 mole) of potassium t-butoxide is combined with 500 ml. of tetrahydrofuran, in a 1 l beaker and 27.0 grams (0.2 mole) of O-ethyl, methylthioformaldoxime is added. The mixture is stirred at room temperature for 15 minutes. 32.6 grams (0.2 mole) of ethyl phosphonothionic dichloride is combined with 200 ml. of tetrahydrofuran in a 1 liter three-neck flask fitted with a stirrer, thermometer and dropping funnel. The solution is cooled in an ice bath and stirred. The oxime salt solution is added over a period of 15 minutes at such a rate that the temperature does not exceed 15C. After the addition is complete, the resulting mixture is stirred at room temperature for one hour, then poured into 400 ml. of benzene. The benzene mixture is washed with two 300 ml. portions of H 0, dried with anhydrous MgSO and evaporated under reduced pressure to yield 46.0 grams (88.3 percent of theory) of O-(O-ethyl-S- methylthioformaldoximino), ethyl, thiophosphonyl chloride. N 1.5370. The compound is characterized by IR.

ethyl EXAMPLE 11 E150 S/OQNO:

C=N()lt O-(O-ethyl-S-methylthioformaldoximino), nitrophenyl)-thionophosphonate Seven grams (0.0503 moles) of 4-nitrophenol is combined with 2.1 grams (0.0503 moles) of caustic and 25 ml. of water in a 500 ml. three-neck flask fitted with a sitter, thermometer, and dropping funnel. The mixture is stirred and 11.5 grams (0.0503 moles) of O- (O-ethyl-S-methylthioformaldoximino), ethylthiophosphoryl chloride, obtained in Example I, in 200 ml. of tetrahydrofuran is added over a period of 30 minutes. The resulting mixture is stirred and heated under reflux for two hours, cooled and poured into 300 ml. of benzene. The benzene mixture is washed with 200 ml. of H 0, 200 ml. dilute NaOH solution, followed by two 200 ml. portions of H 0. The benzene is dried with anhydrous MgSO, and evaporated to yield 11.5 grams (63.1 percent of theory) of the desired compound, O-(O-ethyl-S-methylthioformaldoximino), ethyl-(4-nitrophenyl)-thiophosphonate. The compound is characterized by IR. N 1.5670.

ethyl-(4- EXAMPLE III E120 Cl OCzHs O-ethyl 16.3 grams (0.1 moles) of ethyldichlorophosphate is I combined with 20 ml. of tetrahydrofuran in a 250 ml. three neck flask fitted with a stirrer, thermometer and dropping funnel. The solution is stirred and cooled to 10C. A solution of 13.5 grams (0.1 moles) of O- ethyl, methylthioformaldoxime, 4.0 grams (0.1 moles) of caustic, and 20 ml. of water is added to the stirring solution over a period of 30 minutes. The resulting mixture is stirred for one hour at 0C. and 30 minutes at room temperature until the mixture becomes neutral to pH paper. The mixture is then poured into 300 ml. of Et O and is washed with two ml. portions of H 0. The EL O phase is dried with anhydrous MgSO and evaporated to yield 25.0 grams (96.1% of theory) of the desired compound. N 1.4795. The structure is characterized by IR.

EXAMPLE IV CH: onno 0 ON0z ll C=NO P ems 0 cm,

O-(O-ethyl-S-methylthioformaldoximino), O-ethyl-O- (3-methyl-4-nitrophenyl) phosphate 13.1 grams (0.05 moles) of O-(O-ethylmethylthioformaldoximino), O-ethyl phosphoryl chloride obtained in Example 111 is reacted with 7.65 grams (0.05 moles) of 3-methyl-4-nitrophenol and 2.1 grams (0.0503 moles) of caustic in the same manner as Example 11 to yield 9.5 grams (50.2 percent of theory) of the desired compound. N 1.5254. The compound is characterized by IR.

The following is a table of certain selected compounds that are preparable according to the procedure described hereto. Compound numbers are assigned to each compound and are used throughout the remainder of the application.

in water containing 0.002 percent of a wetting agent,

Sponto 221, (a polyoxyether of alkylated phenols TAB LE I R O\ )C/YR C=N O P Compound Number R1 R: X Y R N13 1 C2115 CH3 @2115 S (EH; 1. 5604 2 a CzHs CH3 CrHs S O 1. 5670 3 C2115 CH3 CzHa S S Q l. 6913 4 CzHs CH3 CzHs S 0 C1 1. 5675 5 Cal-I5 CH3 OCIH5 0 0 $113 1. 5254 6 C2115 CH --OC1H5 O O In 1. 5290 Prepared in Exampio II Prepared in Example IV.

The following tests illustrate the insecticidal and :tcaricidnl activity of the compounds of this invention.

INSECTICIDAL EVALUATION TESTS The following insect species were used in evaluation tests for insecticidal activity:

l.Housefly (HF) Musca domestica (Linn.)

2. German Roach (GR) Blatella germanica (Linn.)

3. Salt-Marsh Caterpillar (SMC) Estigmene acrea y) 4. Lygus Bug (LB) Lygus hesperus (Knight) 5. Bean Aphid (BA) Aphisfabae (Scop.)

The Housefly (HF) was used in evaluation tests of selected compounds as insecticides by the following procedure. A stock solution containing 100 ug/ml of the toxicant in an appropriate solvent was prepared. Aliquots of this solution were combined with 1 milliliter of an acetone-peanut oil solution in an aluminum Petri dish and were allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100 ug per dish to that at which 50 percent mortality was attained. The dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. 25 female houseflies, three to five days old, were introduced into the cage and the percent mortality was recorded after 48 hours. The LD-SO values are expressed in terms of ug per 25 female flies. The result of these insecticidal evaluation tests are given in Table [I under HF.

In the GermanCockroach (GR) tests, one-month old nymphs were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Aliquots of the toxicams, dissolved in an appropriate solvent, were diluted blended with organic sulfonates). Test concentrations ranged from 0.1 percent downward to that at which 50 percent mortality was obtained. Each of the aqueous suspensions of the candidate compounds was sprayed onto the insects through the cloth netting by means of a hand-spray gun. Percent mortality in each case was recorded after 72 hours, and the LD-SO values expressed as percent of toxicant in the aqueous spray were recorded. These values are reported under the columns GR in Table II.

For testing the Salt Marsh Caterpillar, test solutions were prepared in an identical manner and at concentrations the same as. for the German Cockroach above. Sections of bitter dock (Rumex obtuszfolus) leaves, 1 1.5 inches in length, were immersed in the test solutions for 10 to seconds and placed on a wire screen to dry. The dried leaf was placed on a moistened piece of filter paper in a Petri dish and infested with 5-3rd lnstar larvae. Mortality of the larvae was recorded after 72 hours and the LD- values are expressed as percent active ingredient in the aqueous suspension.

The Lygus Bug (LB) Lygus hesperus was tested similarly as the German Cockroach. The caged insects were sprayed with the candidate compounds at concentrations ranging from 0.05 percent downward to that at which 50 percent mortality was obtained. After 24 and 72 hours, counts were made to determine living and dead insects. The LD-50 (percent) values were calculated. These values are reported under the column LB in Table II.

The insect species black bean aphid (BA) Aphis fabae (Scop.) was also employed in the test for insecticidal activity. Young nasturtium (Tropaeolum sp.) plants, approximately 2 to 3 inches tall, were used as the host plants for the bean aphid. The host plant was infested with approximately 50-75 of the aphids. The

placed in the test solution it was infested with the test species. Mortalities were determined after seven days.

Young nasturtium plants were used as the host plants for the bean aphid. The host plants were transplanted tration never exceeded about 1 percent. The toxicants were initially tested at a concentration of 10 parts per million (p.p.m.). Immediately after the host plant was test chemical was dissolved in acetone, added to water into ne p n o Soil that had been treated with the which contained a small amount of Sponto 221, an candidate compound. Immediately after planting in the emulsifying agent. The solution was applied as a spray treated soil the plants were infested with the aphids. to the infested plants. Concentrations ranged from 0.05 Concentrations of toxicant in the soil ranged from percent downward until an LD value was achieved. p.p-m. per pound f Soil downward Until an LD-SO These results are given in Table [I under the l m 10 value was obtained. Mortaility was recorded after 72 BA." hours.

The percentage of kill of each test species was deter- ACARICIDAL EVALUATION TEST mined by comparison with control plants placed in The two-spotted mite (28M), Tetranychus urticae l5 distilled water or untreated soil. The LD-50 values (Koch), was employed in tests for miticides. Young were calculated. These systemic test results are repinto bean plants or lima bean plants (Phaseolus sp.) in ported in Table ll under the columns BA-sys and the primary leaf stage were used as the host plants. The y TABLE IL-LDm VALUES Two-spotted mites HF, GR, LB, SMC, BA, BA-SYS, PE E s, sYs, Compound Number g. percent percent percent percent ppm. percent percent p.p.1n.

Young Pinto been Plants were infested with about 100 30 As those in the art are well aware, various techniques mites of Various ages' Dispersions of candidate are available for incorporating the active component or als were prepared by dissolving 0.1 gram in 10 m o a toxicant in suitable pesticidal compositions. Thus, the suitable solvent, usually acetone. Aliquots of the toxiti id l compositions can b conveniently prepared C Solutions ere p nded in ate C ntaining in the form of liquids or solids, the latter preferably as (3-002 P ce Sponto 221, polyoxyethylene ether homogeneous free-flowing dusts commonly formulated setbltan monolaufete, an emulsifying g the by admixing the active component with finely divided amount of water being sufficient to give concentrations solids or carriers as exemplified by talc, natural clays, of active ingredient ranging from 0.05 percent to that diatomaceous earth, various flours such as walnut shell, at which 50 percent mortality was obtained. The test 40 wheat, soya bean, cottonseed and so forth. suspensions were then sprayed on the infested plants to Liquid compositions are also u f l and normally the P of run After seven days, mortalities of comprise a dispersion of the toxicant in a liquid media, post'embryohie and ovieidal forms were determinedalthough it may be convenient to dissolve the toxicant The Percentage of km was determined y comparison directly in a solvent such as kerosene, fuel oil, xylene, with control Plants which had not been p y w 5 alkylated naphthalenes or the like and use such organic the candidate compounds. The LD-SO values was cal- Solutions di l However h more common culated using well-known procedures. These values are procedure i to employ di i f h toxicant i an reported under the columns 2SM-PE" and 2SM- aqueous media and such compositions may be Tablenproduced by forming a concentrated solution of the toxicant in a suitable organic solvent followed by SYSTEMIC EVALUATION TEST dispersion in water, usually with the aid of surface ac- This test evaluates the root absorption and upward tlVe g The latter, which y be the ahiohie, translocation of the candidate systemic compound.The tiohie, 0f hohiohie yp are exemplified by sodium t -s ott d it (28M), T g h urticae (K h) stearate, potassium oleate and other alkaline metal and the Bean Aphid (BA), Aphis fabae (Scop.) were soaps and detergents such as sodium lauryl sulfate, employed in the test for systemic activity. sodium naphthalene sulfonate, sodium alkyl Young pinto b plants i h primary leaf stage naphthalene, sulfonate methyl cellulose, fatty alcohol were used as host plants for the two-spotted mite. The ethers, p lyglycol fa ty acid esters and other polyoxpinto bean plants were placed in bottles containing 200 yethylene sur a active agents. The proportion of ml. of the test solution and held in place with cotton these agents commonly mprises 1-15 percent by plugs. Only the roots were immersed. The test solutions weight of the p tici al compositions although the prowere prepared b i l i h compounds to be portion is not critical and may be varied to suit any partested in a suitable solvent, usually acetone, and then tleuler sltuatletldiluting with distilled water. The final acetone concen- Iclaim:

l. A process for controlling insects comprising applying thereto an insecticidal amount of a compound having the formula in which X is oxygen or sulfur; Y is oxygen or sulfur; R is alkyl having one to four carbon atoms; R is alkyl having one to four carbon atoms; R is alkyl having one to four carbon atoms or alkoxy having one to four carbon atoms; and R is (l) phenyl, (2) nitrophenyl or (3) trichlorophenyl.

2. The process of claim 1 in which R is ethyl, R is methyl, R is ethyl, X is sulfur, Y is oxygen, and R is 4- nitrophenyl.

3. The process of claim 1 in which R is ethyl, R is methyl, R is ethyl, X is sulfur, Y is sulfur and R is phenyl.

4. A process for controlling acarids comprising applying thereto an acaricidal amount of a compound l0 having the formula v R0 X Y-R \C=N0-1IL/ n s R in which X is oxygen or sulfur; Y is oxygen or sulfur; R is alkyl having one to four carbon atoms; R is alkyl having one to four carbon atoms; R is alkyl having one to four carbon atoms or alkoxy having one to four carbon atoms; and R is (l phenyl, (2) nitrophenyl or (3) trichlorophenyl.

5. The process of claim 4 in which R is ethyl, R is methyl, R is ethyl, X is sulfur, Y is oxygen, and R is 4- nitrophenyl.

6. The process of claim 4 in which R is ethyl, R is methyl, R is ethyl, X is sulfur, Y is sulfur and R is phenyl. 

2. The process of claim 1 in which R is ethyl, R1 is methyl, R2 is ethyl, X is sulfur, Y is oxygen, and R3 is 4-nitrophenyl.
 3. The process of claim 1 in which R is ethyl, R1 is methyl, R2 is ethyl, X is sulfur, Y is sulfur and R3 is phenyl.
 4. A process for controlling acarids comprising applying thereto an acaricidal amount of a compound having the formula
 5. The process of claim 4 in which R is ethyl, R1 is methyl, R2 is ethyl, X is sulfur, Y is oxygen, and R3 is 4-nitrophenyl.
 6. The process of claim 4 in which R is ethyl, R1 is methyl, R2 is ethyl, X is sulfur, Y is sulfur and R3 is phenyl. 